The distorted octahedral complexes [SnCl 4 { n BuSe(CH 2) n Se n Bu}] (n = 2 or 3), (1) and (2), obtained from reaction of SnCl 4 with the neutral bidentate ligands and characterized by IR/Raman and multinuclear (1 H, 77 Se{ 1 H} and 119 Sn) NMR spectroscopy and X-ray crystallography, serve as very effective single source precursors for low pressure chemical vapor deposition (LPCVD) of microcrystalline, single phase tin diselenide films onto SiO 2 , Si and TiN substrates. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) imaging show hexagonal plate crystallites which grow perpendicular to the substrate surface in the thicker films, but align mostly parallel to the surface when the quantity of reagent is reduced to limit the film thickness. X-ray diffraction (XRD) and Raman spectroscopy on the deposited films are consistent with hexagonal SnSe 2 (P3̅ m1; a = b = 3.81 Å; c = 6.13 Å), with strong evidence for preferred orientation of the crystallites in thinner (0.5−2 μm) samples, consistent with crystal plate growth parallel to the substrate surface. Hall measurements show the deposited SnSe 2 is a n-type semiconductor. The resistivity of the crystalline films is 210 (±10) mΩ cm and carrier density is 5.0 × 10 18 cm −3 . Very highly selective film growth from these reagents onto photolithographically patterned substrates is observed, with deposition strongly preferred onto the (conducting) TiN surfaces of SiO 2 /TiN patterned substrates, and onto the SiO 2 surfaces of Si/SiO 2 patterned substrates. A correlation between the high selectivity and high contact angle of a water droplet on the substrate surfaces is observed.